JPH06184089A - New gluocoaminosulfonic acid compound and its production and surfactant composition containing the same - Google Patents

Abstract

PURPOSE:To obtain a new compound having mild action on skin, especially mucosa of eyes, excellent in foaming force and detergency and useful as a surfactant for cleaning hair, face and body. CONSTITUTION:A compound of formula I [R is straight-chain or branched chain 5-22C alkyl, alkenyl, etc.; R' is H or residue obtained by removing glycosidic OH from sugar; (m) is 3 or 4; R'' is H or 1-10C alkyl; (n) is 0-10; M is H or alkali metal, etc.; P is valence of M], e.g. N-(1-deoxy-D-glucitol-1-yl)- N-lauroyl-aminomethanesulfonic acid sodium. This compound is obtained by reacting a fatty acid halide of the formula RCOX (X is halogen) with polyhydroxyaminosulfonic acid of formula II in the presence of an alkali substance (preferably NaOH or KOH), preferably at pH 9-11 and 15-30 deg.C. Furthermore, the fatty acid halide is used in an amount of 1-2.1 times by mol based on the compound of formula II.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a sugar aminosulfonic acid compound useful as a novel surfactant, a method for producing the same, and a surfactant composition containing the same. More specifically, hair having a mild action on the skin and especially on the ocular mucosa, and having excellent foaming power and detergency,
The present invention relates to a sugar aminosulfonic acid compound useful as a surfactant for washing the face and body, a method for producing the same, and a surfactant composition containing the same.

[0002]

2. Description of the Related Art In recent years,
The cleanliness, which is centered on young people, is rapidly spreading, and it is becoming a major social phenomenon. For example, hair washing habits have changed dramatically over the last few years, with most people washing their hair daily. On the other hand, such a change in consciousness toward cleanliness has come to require that surfactants have not only detergency but also low irritation. Also,
Recent increasing environmental awareness has driven the use of natural raw materials in surfactants. Considering these situations together, it is most desirable to effectively utilize reproducible natural raw materials to synthesize a surfactant that is mild to skin and eye mucous membranes.

Alkyl glycosides have heretofore been widely used as surfactants using sugar as a raw material and are known to have low skin irritation. On the other hand, as surfactants using amino acids as raw materials, for example, N-acylated amino acids and the like are known as mild stimulants, but attempts to introduce polyhydroxyl groups to further reduce irritation Only available in aminocarboxylic acid type (Japanese Patent Application No. 3-2796)
No. 86 and No. 4-82044), and the aminocarboxylic acid type had a problem of hard water resistance.

[0004]

[Means for Solving the Problems] The present inventors diligently studied a novel sugar amino acid derivative useful as a mild surfactant to solve the above problems, and as a result, N-acylated derivative of sugar aminosulfonic acid. Was found to have extremely excellent properties as a surfactant, i.e., low irritation to the skin and especially to the ocular mucosa, and having good foaming power, biodegradability and hard water resistance, and the present invention Was completed. That is, the present invention provides a novel sugar aminosulfonic acid compound represented by the general formula (1), a method for producing the same, and a surfactant composition containing the same.

[0005]

[Chemical 3]

[In the formula, R represents a linear or branched alkyl group having 5 to 22 carbon atoms, an alkenyl group, a hydroxyalkyl group, or an alkylphenyl group. R'represents a hydrogen atom or a residue after removing the glycosidic hydroxyl group from the sugar, and (m + 1) R's may be the same or different from each other. m: shows the number of 3 or 4. R ": represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. N: represents a number of 0 to 10. M: a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, a mono atom having 2 to 3 carbon atoms. Represents a di- or trialkanol ammonium, an alkyl group-substituted ammonium having 1 to 5 carbon atoms, or a basic amino acid group, and represents a valence of p: M.] In the general formula (1), R represents a linear or branched chain. Carbon number 5
22 is an alkyl group, an alkenyl group, a hydroxyalkyl group, or an alkylphenyl group. Examples thereof include nonyl group, undecyl group, tridecyl group, pentadecyl group, heptadecyl group, heptadecenyl group, 9-hydroxynonyl group, and 11-hydroxyundecyl group. Group, nonylphenyl group, dodecylphenyl group and the like, and preferably a linear alkyl group having 7 to 21 carbon atoms. R'represents a hydrogen atom or a residue after removing the glycosidic hydroxyl group from the sugar, and examples of the residue after removing the glycosidic hydroxyl group from the sugar include, for example, D-arabinitol group, D-glucitol group, D-
Examples thereof include a mannitol group, a D-galactitol group and a D-maltitol group. It is preferably a hydrogen atom or a D-glucitol group.

Specific examples of the sugar aminosulfonic acid compound represented by the general formula (1) include N- (1-deoxy-D-glucitol-1-yl) -N-lauroyl-aminomethanesulfonic acid sodium salt, N- -(1-Deoxy-D-glucitol-1-yl) -N-lauroyl-2-aminoethanesulfonic acid sodium salt, N- (1-deoxy-D
-Maltitol-1-yl) -N-lauroyl-2-aminoethanesulfonate sodium, N- (1-deoxy-D-glucitol-1-yl) -N-myristoyl-
2-Aminoethanesulfonate sodium, N- (1-deoxy-D-glucitol-1-yl) -N-lauroyl-3-aminopropanesulfonate sodium, N-
(1-deoxy-D-maltitol-1-yl) -N-
Palmitoyl-3-aminopropane sulfonate sodium etc. are mentioned.

The sugar aminosulfonic acid compound represented by the general formula (1) is represented by the general formula (2) RCOX (2) (wherein R represents the same meaning as described above and X represents a halogen atom). A fatty acid halide represented by the general formula (3)

[0009]

[Chemical 4]

Reacting a polyhydroxyaminosulfonic acid represented by the formula (wherein R ', m, R ", n, M and p have the same meanings as described above) in the presence of an alkaline substance. Can be manufactured by.

A fatty acid halide represented by the general formula (2) used in the present invention (hereinafter abbreviated as fatty acid halide (2))
As, for example, capric acid chloride, caproic acid chloride, lauric acid chloride, myristic acid chloride, palmitic acid chloride, oleic acid chloride, single composition fatty acid chloride such as isostearic acid chloride, corresponding fatty acid bromide, coconut oil fatty acid chloride, Examples thereof include fatty acid chlorides having a mixed composition such as beef tallow fatty acid chloride and corresponding fatty acid bromide.

As the other raw material used in the present invention, polyhydroxyaminosulfonic acid represented by the general formula (3) (hereinafter abbreviated as polyhydroxyaminosulfonic acid (3)) is, for example, N- (1 -Sodium deoxy-D-glucitol-1-yl) aminomethanesulfonate, sodium N- (1-deoxy-D-glucitol-1-yl) -2-aminoethanesulfonate, N-
(1-Deoxy-D-maltitol-1-yl) -2-
Aminoethanesulfonic acid sodium salt, N- (1-deoxy-D-maltitol-1-yl) -3-amino-1-
Sodium propane sulfonate, N- (1-deoxy-
D-glucitol-1-yl) -2-amino-1-propanesulfonic acid sodium salt and the like can be mentioned. These polyhydroxyaminosulfonic acids (3) can be prepared, for example, from known monosaccharides, disaccharides or oligosaccharides by a known method (Japanese Patent Laid-Open No.
-95201) and reductive amination with the corresponding aminosulfonic acid.

In the reaction of the present invention, the fatty acid halide (2) is usually used in an amount of 0.9 to 3.0 times, preferably 1.0 to 2.1 times the mol of the polyhydroxyaminosulfonic acid (3). When it is less than this range, a large amount of polyhydroxyaminosulfonic acid (3) remains in the reaction product, and when it is more than this range, a large amount of fatty acid is secondary from the unreacted fatty acid halide (2). To live.

In the reaction of the present invention, in order to secure the reactivity and allow the reaction to proceed to a certain level, an alkaline substance is added to the reaction system so that the pH in the system is on the alkaline side, preferably the pH.
It is desirable to keep it in the range of 9.0 to 11.0. When the pH of the reaction system is lower than this range, hydrogen halide by-produced by the reaction progress and unreacted polyhydroxyaminosulfonic acid (3) form a salt and the reaction does not proceed sufficiently. If the pH of the system is higher than this range, the decomposition of the raw material fatty acid halide (2) is promoted and a large amount of fatty acids are by-produced. As the alkaline substance used, for example, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, inorganic bases such as sodium carbonate, triethylamine,
Examples of the organic base include pyridine and 4- (dimethylamino) pyridine, and sodium hydroxide and potassium hydroxide are particularly practical. The amount of these alkaline substances used is an amount that maintains the reaction system at the above pH.

In the present invention, the reaction temperature is 3 to 50 ° C., especially
15-30 degreeC is preferable. When the temperature is lower than this range, the viscosity in the system increases and the stirring efficiency deteriorates, and when the temperature is higher than this range, the decomposition rate of the raw material fatty acid halide (2) increases remarkably. The fatty acid by-product increases.

The reaction solvent in the present invention is water, or water and ketones such as acetone and methyl ethyl ketone, lower alcohols such as methanol, ethanol and isopropanol, and diols such as 1,3-propanediol and propylene glycol. Any of the mixed solutions with and can be used.

The above general formula obtained by the method of the present invention
The novel sugar aminosulfonic acid compound represented by (1) has excellent surface activity, and the surfactant composition containing such a compound as a main component is excellent in foaming power, detergency and hard water resistance, Since it is hypoallergenic and is mild to the eye mucosa, it can be used not only as a base for washing hair and a base for body washing, but also as a base for washing face.

When this is used as a surfactant composition, the amount used is usually 1 to 100% by weight (calculated as active ingredient). In the above, other components can be used in combination, and examples of such a combination usable are general anionic surfactants (alkyl sulfate ester salt, alkyl ether sulfate ester salt, alkylbenzene sulfonate, α-olefin sulfonate). Salt, alkyl sulfonate, fatty acid glyceride sulfate, alkyl glyceryl ether sulfate,
Fatty acid glyceride sulfonate, alkyl glyceryl ether sulfonate, taurine-based surfactant, sarcosinate-based surfactant, isethionate-based surfactant,
N-acyl acidic amino acid surfactants, higher fatty acid salts, acylated polypeptides, etc.); amphoteric surfactants (alkyl betaine type surfactants, amidopropyl betaine type surfactants, imidazolinium betaine type surfactants, Sulfobetaine type surfactants, phosphobetaine type surfactants and amino acid type surfactants such as sodium laurylaminopropionate, etc .; Nonionic surfactants (coconut oil fatty acid diethanolamide, stearic acid monoglyceride, lauryl dimethylamine oxide) , Polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, fatty acid sorbitan ester, polyoxyethylene fatty acid sorbitan ester, alkyl polyglycoside, etc.); cationic surfactant (stearyl trimethyl ammonium chloride, Distearyl dimethyl ammonium, an ethyl lanolin fatty acid aminopropyl ethyl dimethyl ammonium sulfate), known humectants, thickeners,
Examples thereof include polymer compounds (carboxyethyl cellulose, hydroxyethyl cellulose, cationized cellulose, etc.), perfumes, preservatives and the like.

[0019]

EXAMPLES Next, the present invention will be explained in detail based on examples, but the scope of the present invention is not limited by these.

Example 1 a) Synthesis of sugar taurine Glucose 53.28 g (0.2957 mol), taurine 37.01 g
(0.2957 mol), sodium hydroxide 11.83 g (0.2957 mol), and 5% Pd-carbon (50% hydrous) 4.71 g
The mixture was sealed in a 500 ml autoclave with 0 ml of ion-exchanged water and stirred. After heating to 80 ℃, hydrogen pressure 120k
The reaction was carried out for 5 hours while keeping it constant at g / cm ² . After cooling
The catalyst was filtered off, water was distilled off, and N- (1
Sodium deoxy-D-glucitol-1-yl) -2-aminoethanesulfonate was obtained. Yield 93.44 g (yield 100%), pale yellow solid Amine number analysis value: measured value 166.4 / theoretical value 180.24

[0021]

[Chemical 5]

B) Acylation N- (1-deoxy-D-glucitol-obtained in a)
1-yl) -2-aminoethanesulfonic acid sodium salt 3
0.39 g (0.0976 mol) was stirred at 25 ° C. in a mixed solvent of 30 g of water and 12 g of acetone. To this solution, 44.86 g (0.2051 mol) of lauroyl chloride and a 40% aqueous sodium hydroxide solution were separately added dropwise over 40 minutes while keeping the system pH at 10. The time course of the reaction was followed by HPLC. After aging for 1 hour at room temperature, concentrated hydrochloric acid was added to adjust the pH of the system to 6.
I set it to 7. After removing the reaction solvent, the solid content was washed with ethyl acetate to remove excess fatty acid and the like. Further, once an inorganic salt is removed as an aqueous solution by an electrodialysis method and concentrated again, N- (1-deoxy-
D-glucitol-1-yl) -N-lauroyl-2-
Sodium aminoethane sulfonate was obtained. Yield 38.0 g (79% yield), colorless crystals

[0023]

[Chemical 6]

The measurement results of H ¹ -NMR and IR of the obtained sodium N- (1-deoxy-D-glucitol-1-yl) -N-lauroyl-2-aminoethanesulfonate are shown below. H ¹ -NMR (δ, ppm, heavy water, internal standard; 3- (tris
Methylsilyl) propanesulfonic acid Na): shown in FIG.
You 0.90 (3H, methyl group) 1.3 (16H, lauroyl group methylene) 1.6 (2H, lauroyl group methylene, amide β position) 2.45 (2H, lauroyl group methylene, amide α position) 3.2 (2H, sulfonyl group α position) 3.5 ~ 4.1 (10H, sulfonyl group β-position, glucitol hydrogen) IR (cm ^-1 , KBr tablet): shown in FIG.

3406 (OH), 2920, 2848, 1740, 1629 (amide), 1467, 1188, 1050 Example 2 a) Synthesis of sugar aminopropanesulfonic acid Maltose 50.00 g (0.1461 mol), 3-amino-1-
Sodium propanesulfonate dihydrate 28.80 g (0.14
61 mol), and 3.52 g of 5% Pd-carbon (50% water content)
Was sealed in a 500 ml autoclave together with 200 ml of ion-exchanged water and stirred. After heating to 80 ℃, hydrogen pressure
The reaction was carried out for 5 hours while keeping it constant at 120 kg / cm ² . After cooling, the catalyst was filtered off and water was distilled off to give N- represented by the following formula.
(1-Deoxy-D-maltitol-1-yl) -3-
Obtained sodium aminopropane sulfonate. Yield 64.09g (90% yield), pale yellow solid

[0026]

[Chemical 7]

B) Acylation N- (1-deoxy-D-maltitol-obtained in a)
1-yl) -3-aminopropanesulfonic acid sodium salt
30.40 g (0.0624 mol) was stirred at 25 ° C. in a mixed solvent of 30 g of water and 12 g of acetone. To this solution, 23.90 g (0.0748 mol) of palmitoyl bromide and 40% aqueous sodium hydroxide solution were separately added dropwise over 40 minutes while maintaining the system pH at 10. The time course of the reaction was followed by HPLC. After aging for 1 hour at room temperature, add concentrated hydrochloric acid to adjust the pH of the system.
I set it to 6.7. After removing the reaction solvent, the solid content was washed with ethyl acetate to remove excess fatty acid and the like. Further, once an inorganic salt is removed as an aqueous solution by an electrodialysis method and then concentrated again, N- (1-deoxy-D-maltitol-1-yl) -N-palmitoyl-3- is represented by the following formula. Obtained sodium aminopropane sulfonate. Yield 38.0 g (79% yield), colorless crystals

[0028]

[Chemical 8]

The H ¹ -NMR and IR measurement results of the obtained sodium N- (1-deoxy-D-maltitol-1-yl) -N-palmitoyl-3-aminopropanesulfonate are shown below. H ¹ -NMR (δ, ppm, heavy water, internal standard; 3- (tris
Methylsilyl) propanesulfonic acid Na) : 0.92 (3H, methyl group) 1.3 (24H, palmitoyl group methylene) 1.6 (2H, palmitoyl group methylene, amide β position) 2.40 (2H, palmitoyl group methylene, amide α position) 3.0 (2H , Sulfonyl group α-position) 3.5 to 4.1 (19H, sulfonyl group β, γ-position, maltitol hydrogen) IR (cm ^-1 , KBr tablet): 3450 (OH), 2950, 1740, 1625 (amide), 1200 Test Example N- (1-deoxy-D-glucitol-1-yl) -N-lauroyl-2-aminoethanesulfonate sodium obtained in Example 1 and N-obtained in Example 2
(1-deoxy-D-maltitol-1-yl) -N-
With respect to sodium palmitoyl-3-aminopropanesulfonate, an irritation test and a foaming power test were conducted by the following methods. Further, as control compounds, sulfomonoalkyl (C ₁₂ ) succinate (SS, control compound 1), alkyl (C ₁₀ ) glucoside (AG, control compound 2), which have been known to be extremely mild to the skin, are conventionally used. And N-lauroyl-N-methyltaurine (AMT, control compound 3) were selected, and the irritation test and the foaming power test were conducted in the same manner. The results are shown in Table 1.

<Test Method for Irritation> As a test method for irritation, a cytotoxicity test correlated with ocular mucosal irritation was carried out. That is, SIRC (cells derived from rabbit cornea) was incubated at 37 ° C for 50
A surfactant was added to the precultured for 2 days under the condition of% CO ₂ humid gas phase, and the mixture was further cultured for 2 days under the same conditions. After that, methanol was added dropwise to fix it, and Giemsa staining was performed, and the absorbance was measured to determine an IC ₅₀ value (concentration at which 50% of cells were engrafted). As a guideline for evaluation of measurement values, less than 30ppm is strong irritation, 30ppm or more and less than 300ppm is moderate irritation, 300p
There is low irritation above pm.

<Testing Method for Foaming Power> The surfactant was diluted to 40% by diluting with 4 ° DH hard water so that the concentration by weight was 1.0%. The measurement was carried out by an inversion stirring method, and after stirring for 30 seconds, the amount of foam (ml) after standing for 10 seconds was measured.

[0032]

[Table 1]

[Brief description of drawings]

FIG. 1 shows N- (1-deoxy-D obtained in Example 1.
-Glucitol-1-yl) -N-lauroyl-2-aminoethanesulfonate sodium ¹ H-NMR spectrum.

FIG. 2 shows N- (1-deoxy-D obtained in Example 1).
1 is an IR spectrum of sodium glucitol-1-yl) -N-lauroyl-2-aminoethanesulfonate.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location // A61K 7/075 8615-4C 7/50 9283-4C

Claims (3)

[Claims] 1. A novel sugar aminosulfonic acid compound represented by the general formula (1). [Chemical 1] [In the formula, R represents a linear or branched alkyl group having 5 to 22 carbon atoms, an alkenyl group, a hydroxyalkyl group, or an alkylphenyl group. R'represents a hydrogen atom or a residue after removing the glycosidic hydroxyl group from the sugar, and (m + 1) R's may be the same or different from each other. m: shows the number of 3 or 4. R ": represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. N: represents a number of 0 to 10. M: a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, a mono atom having 2 to 3 carbon atoms. , Di- or trialkanol ammonium, an alkyl group-substituted ammonium having 1 to 5 carbon atoms, or a basic amino acid group. 2. A fatty acid halide represented by the general formula (2) RCOX (2) (wherein R represents the same meaning as described above and X represents a halogen atom) and a general formula (3) 2] (Wherein R ′, m, R ″, n, M and p have the same meanings as described above), and are reacted with polyhydroxyaminosulfonic acid in the presence of an alkaline substance. The method for producing the sugar aminosulfonic acid compound according to claim 1. 3. A surfactant composition comprising the sugar aminosulfonic acid compound according to claim 1.